CN104617265B - Method for preparing silica carbon composite lithium ion battery cathode material - Google Patents
Method for preparing silica carbon composite lithium ion battery cathode material Download PDFInfo
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- CN104617265B CN104617265B CN201510009734.0A CN201510009734A CN104617265B CN 104617265 B CN104617265 B CN 104617265B CN 201510009734 A CN201510009734 A CN 201510009734A CN 104617265 B CN104617265 B CN 104617265B
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 46
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 27
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 239000010406 cathode material Substances 0.000 title claims abstract description 16
- 238000000498 ball milling Methods 0.000 claims abstract description 97
- 239000000463 material Substances 0.000 claims abstract description 38
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 239000007789 gas Substances 0.000 claims description 22
- 238000000137 annealing Methods 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 239000002585 base Substances 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 7
- 229910021332 silicide Inorganic materials 0.000 claims description 6
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910021350 transition metal silicide Inorganic materials 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 23
- 238000005516 engineering process Methods 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- 238000010301 surface-oxidation reaction Methods 0.000 abstract description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011247 coating layer Substances 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 2
- 239000002210 silicon-based material Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 23
- 238000001228 spectrum Methods 0.000 description 14
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 12
- 229910052710 silicon Inorganic materials 0.000 description 12
- 230000004087 circulation Effects 0.000 description 11
- 239000007795 chemical reaction product Substances 0.000 description 10
- 230000002441 reversible effect Effects 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- 238000001069 Raman spectroscopy Methods 0.000 description 9
- 229910012506 LiSi Inorganic materials 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 229910005001 Li12Si7 Inorganic materials 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 5
- 238000003701 mechanical milling Methods 0.000 description 5
- 229910007562 Li2SiO3 Inorganic materials 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000011863 silicon-based powder Substances 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 229910018557 Si O Inorganic materials 0.000 description 3
- 229910003481 amorphous carbon Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 229910052909 inorganic silicate Inorganic materials 0.000 description 3
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910017113 AlSi2 Inorganic materials 0.000 description 1
- 229910010029 Li2MgSi Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001556 Li2Si2O5 Inorganic materials 0.000 description 1
- 229910010100 LiAlSi Inorganic materials 0.000 description 1
- 229910019752 Mg2Si Inorganic materials 0.000 description 1
- 229910006140 Si70Sn30 Inorganic materials 0.000 description 1
- 229910020489 SiO3 Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- 238000013486 operation strategy Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Silicon Compounds (AREA)
Abstract
The invention discloses a method for preparing a silica carbon composite lithium ion battery cathode material. The method comprises the following steps: in the CO2 gas atmosphere, ball-milling silica-based materials, and finally obtaining the silica carbon composite material. The composite material prepared by the method contains a silicon oxide, silicate, carbonate and a carbon coating layer. The method is a technology integrating composite material preparation, surface oxidation modification and surface carbon-coating, and the modified silicon-based compound lithium ion battery cathode material has good performances and a wide application prospect.
Description
Technical field
The present invention relates to lithium ion battery negative material field, and in particular to a kind of silica carbon composition lithium ion battery cathode
The preparation method of material.
Background technology
With the development and the progress of human society of science and technology, lack of energy and problem of environmental pollution are increasingly highlighted, and exploitation is new
Type is efficiently, the energy of cleaning is converted, memory technology and energy utilization mode become these problems of solution and realize that human society can
The key of sustainable development.Lithium ion battery with its high workload current potential, high-energy-density density, high-specific-power, elevated operating temperature scope,
Long circulation life and preferable environment friendly, in Portable mobile electronic device field, electric tool, energy storage device, electricity
Motor-car and field of hybrid electric vehicles are widely used.The especially in the past few years fast development of electric automobile and electronic equipment
Miniaturization, lightness, put forward higher requirement to lithium ion battery, and exploitation new type of safe is efficient, high power capacity, high magnification, length
The lithium ion battery of cycle life becomes the focus of current research, and electrode material is the decisive of decision performance of lithium ion battery
Factor, is also the difficult point and technological core of lithium ion battery exploitation.
In order to improve the overall performance of lithium ion battery, numerous new electrode materials are developed.Wherein Si negative poles are with its pole
High theoretical specific capacity (3579 per gram of MAH) receives much concern, but capacity declines caused by huge change in volume (300%)
The problem of moving back becomes the main obstruction for realizing its commercial applications.Research shows that Si surfaces occur oxidation can form one layer of amorphous state
SiOxPassivation layer.SiOxCan react to form irreversible Li with Li after embedding lithium first2O、Li4SiO4And it is reversible
Li2Si2O5And Si, and irreversible Li2O and Li4SiO4Then can mutually alleviate, absorb the volumetric expansion of Si as inertia, therefore
One layer of SiO that Si surfaces are formedxLayer can be effectively improved the performance of Si negative poles.Not only can strengthen in addition, compound with material with carbon element
The electric conductivity of material, moreover it is possible to the volumetric expansion of padded coaming, so as to be effectively improved the cyclical stability of material.Obviously, one is developed
Plant Si@SiOx/ C cathode composites system can effectively improve the chemical property of Si base negative poles.
Silicon/carbon composite species is various, including cladded type (hud typed, fibrous type and porous type), embedded type and dispersion
Type.Introducing the method for material with carbon element at present mainly has following several：Chemical vapor deposition, spray drying, spray pyrolysis, high warm
Solution, electrostatic spinning, hydro-thermal method, template etching etc..Have in the method for Si Surface coating inert layers：Logical O2High-temperature heat treatment, liquid phase
Method, sol-gel process etc..These method tedious process, high cost, high energy consumption, poor controllability, operation strategies are narrow.It is prior
It is that the surface oxidation of Si is separately carried out with carbon coating technique and technique can not be compatible, it is impossible to while for preparing Si@SiOx/ C is multiple
Compound system.Therefore, the good complex Si@SiO of a kind of convenient, inexpensive, environmental friendliness, controllability are developedxIt is prepared by/C systems
The scientific research meaning of technique and economic benefit are obvious；This technology of preparing can enrich the preparation side of composite
Method, this Si@SiOx/ C complex systems can widen novel high-capacity lithium ion battery material species system.
The content of the invention
The invention provides a kind of simple to operate, efficiently, controllability is strong, low energy consumption, and silica carbon applied widely is combined
The preparation method of lithium ion battery negative material.Composite materials obtained in the preparation method contain Si oxide, silicate, carbon
Hydrochlorate and carbon coating layer, are the technologies of a kind of bonded composite preparation, Surface Oxidation Modification and material with carbon-coated surface feature, and Jing changes
The silicon substrate complex lithium ion battery cathode material of property has excellent performance and wide application prospect.
A kind of preparation method of silica carbon composition lithium ion battery cathode material, comprises the following steps：In CO2Atmosphere
Under, silica-base material ball milling obtains silica carbon composite.
After silica-base material is added in ball grinder, CO is passed through2Gas, then carries out ball milling, and silica-base material is in ball milling mistake
Cheng Zhonghui and CO2Gas reaction generates SiOxAnd carbon, and with the prolongation of Ball-milling Time, SiOxCan gradually increase with the content of carbon, shape
Into SiOxWith the clad of carbon, the clad can effectively alleviate volumetric expansion of the silicon in charge and discharge process, so as to improve silicon
The cyclical stability of sill.
Described silica carbon composite (abbreviation Si@SiOx/ C complex) can be used as the negative material of lithium ion battery.
Described silica-base material is elementary silicon, alkali metal silicide, alkaline earth metal silicide, Group IIIA silicide or transition metal silication
Thing.
Preferably, the silica-base material and CO2The mol ratio of gas is 0.001~100: 1.The mol ratio is excessive, instead
Should be incomplete, coating thickness is limited, and affects the performance of material；Mol ratio is too small, CO2Excessive, clad is blocked up, deteriorates material
Performance.
Preferably, CO2The pressure of gas is 0.1~50bar；It is further preferred that 0.1~20bar.CO2The pressure of gas is too
It is low, easily cause reaction rate slowly, the SiO of formationxIt is low with the content of the carbon of deposition, and energy consumption is big；CO2The pressure of gas is too big, right
The air-tightness of reactor has high demands, and there is potential safety hazard.
The time of ball milling generally can be according to the different and different of silica-base material, preferably, the time of the ball milling is 0.5
~24h, temperature is 10~40 DEG C.
The mode of the ball milling only needs that mechanization educational level can be provided, it is preferable that described ball milling includes planetary
Ball milling, vibration type ball milling or horizontal planetary ball milling.
Preferably, when the ball milling is planetary type ball-milling or horizontal planetary ball milling, ball milling condition is：Ratio of grinding media to material be 20~
100: 1, rotational speed of ball-mill is 200~500 revs/min, and Ball-milling Time is 0.5~24h.In the ratio of grinding media to material, rotational speed of ball-mill and ball
In time consuming, it is ensured that the efficiency of grinding, the impact grinding effect of abrading-ball is given full play to, make silica-base material and CO2Gas fills
Divide reaction, obtain the SiO of optimum thicknessxAnd carbon coating layer.Preferably, when the ball milling is vibration type ball milling, ball milling condition
For：Ratio of grinding media to material is 20~100: 1, and frequency of vibration is 1200 cycle per minute clocks, and Ball-milling Time is 0.5~24h.
The silica carbon composite obtained after ball milling is made annealing treatment.Product after ball milling can be in vacuum, argon, nitrogen
Made annealing treatment under gas or acetylene atmosphere.The temperature of the annealing is 550~1200 DEG C, and the time of annealing is 0.1~12h.
The amorphous SiO for being formed is caused in this annealing temperature and time rangexDeng material part crystallization, or secondary bag carbon is carried out, it is excellent
Change product property.Annealing temperature is too high, and overlong time can cause the particle agglomeration that ball milling is refined, or the carbon of ball milling deposition to steam,
It is unfavorable for the optimization of product property.
Compared with prior art, the invention has the advantages that：
(1) preparation method of the present invention is simple, it is easy to operate, with low cost, and energy consumption is low, and the CO produced after ball milling both can make
For the shielding gas in annealing process, but also as fuel recovery, further reducing energy consumption is environmentally friendly；
(2) present invention is combined the preparation of composite, Surface Oxidation Modification and material with carbon-coated surface technique, realizes
The inertia such as Si oxide, silicate, carbonate cladding is synchronous with carbon coating；
(3) yield of the silica carbon composite obtained by is high, and good dispersion, clad is uniform；
(4) the silica carbon composite obtained by is high with capacity as ion secondary battery cathode material lithium, coulombic efficiency
Height, the advantage of good cycling stability.
Description of the drawings
Fig. 1 is the collection of illustrative plates of the product of the embodiment of the present invention 1；
A () is X-ray diffraction spectrum；B () is infared spectrum；C () is Raman collection of illustrative plates；
Fig. 2 is the stable circulation linearity curve of the product of the embodiment of the present invention 1；
Fig. 3 is the X-ray diffraction spectrum of the annealed product of the embodiment of the present invention 1；
Fig. 4 is the cyclical stability contrast of product before and after the annealing of the embodiment of the present invention 1；
Fig. 5 is the collection of illustrative plates of the product of the embodiment of the present invention 2；
A () is X-ray diffraction spectrum；B () is infared spectrum；C () is Raman collection of illustrative plates；
Fig. 6 is that the product of the embodiment of the present invention 2 is contrasted with the cyclical stability of the end-product of embodiment 1；
Fig. 7 is the collection of illustrative plates of the product of the embodiment of the present invention 3；
A () is X-ray diffraction spectrum；B () is infared spectrum；C () is Raman collection of illustrative plates；
Fig. 8 is the product of the embodiment of the present invention 3 and embodiment 1, the cyclical stability contrast of 2 end-products；
Fig. 9 is the stable circulation linearity curve of the product of the embodiment of the present invention 3.
Specific embodiment
Embodiment 1
Micron silicon and CO2Mol ratio is 1.73: 1.In argon gas atmosphere glove box, micron order (1.06 μm) pure silicon powder is weighed
2g, loads ball grinder, and ratio of grinding media to material (mass ratio) is 84: 1, and abrading-ball is stainless steel ball, ball grinder evacuation.Ball grinder volume used
For 170 milliliters, added CO can be extrapolated according to The Ideal-Gas Equation pV=nRT2Pressure be 6bar.In evacuation
The high-purity CO of 6bar are filled in ball grinder2.Ball grinder is placed on planetary ball mill, with 400 revs/min of rotating speed ball milling 0.5~
24 hours, gained sample took out in the glove box of argon gas atmosphere, obtained generated in-situ Si@SiOx/ C complex.
Take the CO of above-mentioned 2g micron silicons and 6bar2The product 2g of ball milling 6h, in being placed in corundum crucible, then corundum crucible is put
In tube furnace, using Ar as protective atmosphere, 800 degrees Celsius are risen to the heating rate of 3 degrees celsius/minutes, be incubated 3h, then
Cool to room temperature with the furnace, obtain the partially-crystallized Si@SiO of clad2/ C complex.
Fig. 1 (a) is micron order (1.06 μm) pure silicon powder 2g, in 6bar CO2, ratio of grinding media to material 84: 1, abrading-ball is stainless steel ball,
400 revs/min of rotational speed of ball-mill, the X-ray diffraction of difference ball milling material after 0.5 hour, 2 hours, 4 hours, 6 hours and 8 hours
Spectrum.It can be seen that as Ball-milling Time increases, peak species is almost unchanged, the peak of Si is, and peak intensity declines, peak
Width broadens, and illustrates that long-time ball milling causes Si from crystal to amorphous transition.
Fig. 1 (b) is the infared spectrum of ball milling end-product.1090cm in product after ball milling in figure-1, 800cm-1, 480cm-1Place
Have obvious absworption peak, these peaks represent the presence of Si-O keys, illustrate Si powder in mechanical milling process with CO2Reaction generates SiOx,
And as Ball-milling Time increases, SiOxAmount increase.
Fig. 1 (c) is the Raman collection of illustrative plates of ball milling end-product.In 510cm-1, 290cm-1, 950cm-1Neighbouring peak is the drawing of Si
Graceful peak position, 1380cm-1And 1560cm-1Peak correspond to respectively the D peaks of amorphous carbon and graphited G peaks.Illustrate Si powder in ball milling
During with CO2Reaction also generates carbon, and in addition with the prolongation of Ball-milling Time, D peaks and G peaks are more and more obvious, illustrates reaction
As the prolongation reaction of Ball-milling Time is more abundant, the carbon amounts of generation is consequently increased.
Fig. 2 is micron Si respectively in Ar and CO2The middle ball milling cyclical stability of 4 hours and coulombic efficiency are contrasted.As a result
Show there is SiOxHave compared to the uncoated Si cyclical stabilities of identical particle size with the Si of C clads and be obviously improved.30
After individual circulation, the charge specific capacity of Si@SiOx/C complex is every gram of silicon of 1575.7 MAH, reversible capacity conservation rate
(68.5%) the reversible capacity conservation rate (23.33%) far above pure Si.Due to SiOxWith the presence of C clads so as to first
(88%) of the coulombic efficiency (78.9%) less than pure Si, this is due to SiOxMiddle amorphous SiO2Li is formed in process of intercalation4SiO4
Reason, and first after coulombic efficiency be stably held in 98% or so, better than the coulombic efficiency of uncoated Si.
Fig. 3 is the CO of 2g micron silicons and 6bar2XRD spectrum before the product annealing of ball milling 6h and after annealing.Can from figure
Sample after to find out annealing has obvious SiO2Diffraction maximum, illustrates there is the SiO of amorphous in the clad that ball milling is generatedxInto
Point, its crystallization is made by annealing.
Fig. 4 is the CO of 2g micron silicons and 6bar2Cycles samples stability pair before the product annealing of ball milling 6h and after annealing
Than.As a result show, the initial discharge specific capacity of sample decreases after annealing, this is because amorphous SiOxCan be and brilliant with embedding lithium
The SiO of state2Not embedding lithium causes capacitance loss.And anneal after cycles samples stability compared with annealing before make moderate progress, this is
Because the SiO of crystalline state2The volumetric expansion of Si can be more effectively buffered, in addition, there is the dismutation reaction of SiO in annealing process
So that clad has the nanocrystalline of Si, the also improvement for product circulation stability contributes.
Embodiment 2
In argon gas atmosphere glove box, LiH and Si sample being weighed at 1: 7 in molar ratio, loading ball grinder, ratio of grinding media to material is 30:
1, abrading-ball is zirconia ball.The ball grinder for filling LiH and Si mixture is placed on planetary ball mill, with 300 revs/min
Rotating speed ball milling 2 hours.Heating is carried out in ball milling product vacuum atmosphere and puts hydrogen, heating rate is 5 degrees celsius/minutes, heating-up temperature
For 530 degrees Celsius, 4 hours are incubated, in holding stage, system evacuation once, are then cooled to room temperature every 0.5 hour.
The mixture of Si and Li-Si alloys is obtained, LiSi is designated as7。
LiSi7With CO2Mol ratio is 0.24: 1.The LiSi of 1g is weighed in argon gas atmosphere glove box7, load ball grinder, ball
Than being 84: 1, abrading-ball is stainless steel ball to material, ball grinder evacuation.Ball grinder volume used is 170 milliliters, according to ideal gases shape
State equation pV=nRT can extrapolate added CO2Pressure be 3bar.The high-purity CO of 3bar are filled in the ball grinder of evacuation2.Will
Ball grinder is placed on planetary ball mill, and with 400 revs/min of rotating speed ball milling 1~24 hour, gained sample is in argon gas atmosphere
Take out in glove box, obtain generated in-situ Si@SiOx/ C complex.
Fig. 5 (a) is the LiSi of 1g7With the CO of 3bar2Difference ball milling 0 hour, 1 hour, 4 hours, 6 hours, 8 hours and 12
The X-ray diffraction spectrum of end-product after hour.As seen from the figure, the LiSi that prepared by hydrogen discharge reaction7The mainly composition of Si, also pole
A small amount of Li12Si7Alloy, with CO2After ball-milling reaction, Li12Si7The peak of alloy all disappears, and illustrates itself and CO2Fully reaction.With
The prolongation of Ball-milling Time, peak species is almost unchanged, is the peak of Si, and peak intensity declines, and peak width broadens, and illustrates long-time ball milling
So that Si is from crystal to amorphous transition.
Fig. 5 (b) is the LiSi of 1g7With the CO of 3bar2Difference ball milling 0 hour, 1 hour, 4 hours, 6 hours, 8 hours and 12
The infared spectrum of end-product after hour.1090cm in product after ball milling in figure-1, 480cm-1Nearby there is obvious absworption peak, these
Peak represents the presence of Si-O keys, illustrates LiSi7With CO in mechanical milling process2Reaction generates SiOx, and as Ball-milling Time increases
It is long, SiOxAmount increase.
Fig. 5 (c) is the LiSi of 1g7With the CO of 3bar2Difference ball milling 0 hour, 1 hour, 4 hours, 6 hours, 8 hours and 12
The Raman collection of illustrative plates of end-product after hour.In 510cm-1, 290cm-1, 950cm-1Neighbouring peak is the Raman peak position of Si, 1380cm-1
And 1560cm-1Peak correspond to respectively the D peaks of amorphous carbon and graphited G peaks.Illustrate LiSi7With CO in mechanical milling process2Instead
Carbon should be also generated, in addition with the prolongation of Ball-milling Time, D peaks and G peaks are more and more obvious, illustrate reaction with Ball-milling Time
Extend reaction more fully, the carbon amounts of generation is consequently increased.
Li elements and CO2The product of reaction is likely to form ionic compound, it is impossible to show in infrared and Raman collection of illustrative plates
Out.
Fig. 6 is in CO2The middle ball milling LiSi of 4 hours7With respectively in CO2With the cyclical stability of the Si of 4 hours of ball milling in Ar
And coulombic efficiency contrast.As a result illustrate, the addition of Li elements makes itself and CO2Enrich after reaction Si surfaces clad into
Point, so as to significantly more efficient its volume expansion of suppression.After 32 circulations, LiSi7With CO2The charge specific capacity of 4 hours products of ball milling is
1929.7 every gram of MAH silicon, reversible capacity conservation rate is 80.9%, higher than pure Si and CO2The reversible appearance of 4 hours products of ball milling
Amount conservation rate 68.5%.
Embodiment 3
In argon gas atmosphere glove box, LiH and Si sample being weighed at 2: 7 in molar ratio, loading ball grinder, ratio of grinding media to material is 30:
1, abrading-ball is zirconia ball.The ball grinder for filling LiH and Si mixture is placed on planetary ball mill, with 300 revs/min
Rotating speed ball milling 2 hours.Heating is carried out in ball milling product vacuum atmosphere and puts hydrogen, heating rate is 5 degrees celsius/minutes, heating-up temperature
For 530 degrees Celsius, 6 hours are incubated, in holding stage, system evacuation once, are then cooled to room temperature every 0.5 hour.
The mixture of Si and Li-Si alloys is obtained, Li is designated as2Si7。
Li2Si7With CO2Mol ratio is 0.23: 1.The Li of 1g is weighed in argon gas atmosphere glove box2Si7, load ball grinder,
Ratio of grinding media to material is 84: 1, and abrading-ball is zirconia ball, ball grinder evacuation.Ball grinder volume used is 170 milliliters, according to ideal gases
State equation pV=nRT can extrapolate added CO2Pressure be 3bar.The high-purity CO of 3bar are filled in the ball grinder of evacuation2。
Ball grinder is placed on planetary ball mill, with 400 revs/min of rotating speed ball milling 1~24 hour, gained sample is in argon gas atmosphere
Glove box in take out, obtain generated in-situ Si@SiO2/Li2SiO3/ C complex.
Fig. 7 (a) is the Li of 1g2Si7With the CO of 3bar2Difference ball milling 0 hour, 1 hour, 4 hours, 6 hours, 8 hours and 12
The X-ray diffraction spectrum of end-product after hour.As seen from the figure, the Li that prepared by hydrogen discharge reaction2Si7Mainly the composition of Si, also few
Amount Li12Si7Alloy, compared to LiSi7, Li2Si7Middle Li12Si7The peak of alloy becomes apparent from, and illustrates that Li contents increase and causes
Li12Si7The content of alloy is improved.The ball milling Li of 1 hour2Si7Product in have SiO2And Li2SiO3Peak, illustrate a small amount of
Li12Si7Alloy and CO2There is chemical reaction in ball milling, make have Li in product2SiO3, the addition of Li elements enrich clad into
Point.
Fig. 7 (b) is the Li of 1g2Si7With the CO of 3bar2Difference ball milling 0 hour, 1 hour, 4 hours, 6 hours, 8 hours and 12
The infared spectrum of end-product after hour.1090cm in product after ball milling in figure-1, 480cm-1Nearby there is obvious absworption peak, these
Peak represents the presence of Si-O keys, illustrates Li2Si7With CO in mechanical milling process2Reaction generates SiOx, and with Ball-milling Time
Increase, SiOxAmount increase.
Fig. 7 (c) is the Li of 1g2Si7With the CO of 3bar2Difference ball milling 0 hour, 1 hour, 4 hours, 6 hours, 8 hours and 12
The Raman collection of illustrative plates of end-product after hour.In 510cm-1, 290cm-1, 950cm-1Neighbouring peak is the Raman peak position of Si, 1380cm-1
And 1560cm-1Peak correspond to respectively the D peaks of amorphous carbon and graphited G peaks.Illustrate Li2Si7With CO in mechanical milling process2Instead
Carbon should be also generated, in addition with the prolongation of Ball-milling Time, D peaks and G peaks are more and more obvious, illustrate reaction with Ball-milling Time
Extend reaction more fully, the carbon amounts of generation is consequently increased.
Fig. 8 is in CO2The middle ball milling Li of 4 hours2Si7With LiSi7And in CO2With the circulation of the Si of 4 hours of ball milling in Ar
Stability and coulombic efficiency are contrasted.As a result illustrate, the content of Li increases the clad for causing Si surfaces under ball milling same time
Thickness increases, due to having more Si for forming SiO2And Li2SiO3, so Li2Si7The Capacity Ratio pure Si and LiSi of product7
It is low.The increase of the abundant and thickness of cladding composition of layer makes it more effectively inhibit the volumetric expansion in Si charge and discharge process,
Make product circulation stability more excellent, after 32 circulations, Li2Si7With CO2The charge specific capacity of 4 hours products of middle ball milling is 1111.9
Every gram of silicon of MAH, reversible capacity conservation rate is 85.9%, higher than LiSi7With pure Si and CO24 hours products of middle ball milling it is reversible
Capability retention (80.9% and 68.5%).
Fig. 9 is Li2Si7In CO2The cyclical stability contrast of middle ball milling different time product.Li2Si7With CO2Difference ball milling 1
Hour, the reversible capacity conservation rate after the product of 6 hours, 8 hours and 12 hours is circulated at 55 is respectively 69.3%,
74.5%, 78.5% and 90.7%.As a result illustrate, with the prolongation of Ball-milling Time, clad is thicker, the volumetric expansion to Si presses down
Effect processed is more obvious.The Si@SiO that wherein ball milling is obtained for 12 hours2/Li2SiO3/ C complex reversible capacity after 67 circulations is protected
Holdup is up to 87.2%, shows extremely excellent cyclical stability.
Embodiment 4~15
It is identical with the preparation method of embodiment 3, corresponding change is only made to ball milling preparation condition, obtain Si, Li2MgSi、
Mg2Si、FeSi4、Li5AlSi2、Li8Al3Si5、LiAlSi、CrSi5、Al73Si25Ni2、Al74Si25Cu、Ti25Si75、Si70Sn30
With CO2The corresponding complexes that ball-milling reaction is generated.Table 1 is listed using the stainless steel jar mill that volume is 170 milliliters, different silicon
Base negative material and CO2Reaction condition and product 50 circulation after reversible capacity conservation rate.
Table 1
Claims (9)
1. a kind of preparation method of silica carbon composition lithium ion battery cathode material, it is characterised in that comprise the following steps：In CO2
Under atmosphere, silica-base material ball milling obtains silica carbon composite；
The silica-base material is alkali metal silicide, alkaline earth metal silicide, Group IIIA silicide or transition metal silicide.
2. the preparation method of silica carbon composition lithium ion battery cathode material as claimed in claim 1, it is characterised in that described
Silica-base material and CO2The mol ratio of gas is 0.001~100:1.
3. the preparation method of silica carbon composition lithium ion battery cathode material as claimed in claim 1, it is characterised in that CO2Gas
The pressure of body is 0.1~50bar.
4. the preparation method of silica carbon composition lithium ion battery cathode material as claimed in claim 1, it is characterised in that described
The time of ball milling is 0.1~24h, and temperature is 10~40 DEG C.
5. the preparation method of silica carbon composition lithium ion battery cathode material as claimed in claim 1, it is characterised in that described
Ball milling include planetary type ball-milling, vibration type ball milling or horizontal planetary ball milling.
6. the preparation method of silica carbon composition lithium ion battery cathode material as claimed in claim 5, it is characterised in that described
When ball milling is planetary type ball-milling or horizontal planetary ball milling, ball milling condition is：Ratio of grinding media to material is 20~100:1, rotational speed of ball-mill be 200~
500 revs/min, Ball-milling Time is 0.5~24h；When the ball milling is vibration type ball milling, ball milling condition is：Ratio of grinding media to material be 20~
100:1, frequency of vibration is 800-1200 cycle per minute clocks, and Ball-milling Time is 0.5~24h.
7. the preparation method of silica carbon composition lithium ion battery cathode material as claimed in claim 1, it is characterised in that by ball
The silica carbon composite obtained after mill is made annealing treatment.
8. the preparation method of silica carbon composition lithium ion battery cathode material as claimed in claim 7, it is characterised in that described
The process of annealing is carried out under vacuum, argon, nitrogen or acetylene atmosphere.
9. the preparation method of silica carbon composition lithium ion battery cathode material as claimed in claim 7, it is characterised in that described
The temperature of annealing is 550~1200 DEG C, and the time of annealing is 0.1~12h.
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